Triazinyl-anthraquinone dyestuffs



United States Patent C) 3,499,896 TRlAZINYL-ANTHRAQUINONE DYESTUFFS Rutger Neeif, Leverkusen, Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed June 8, 1967, Ser. No. 644,475 Claims priority, application Germany, June 15, 1966, F 49,473 Int. Cl. C07d 55/20 US. Cl. 260249 10 Claims ABSTRACT OF THE DISCLOSURE Anthraquinone dyestuffs containing an a-amino-triazine substituent wherein the triazine ring is substituted by alkoxy, aralkoxy, alkenyloxy, aralkenyloxy, or cyclohexoxy groups, are useful for dyeing synthetic fiber materials.

DISCLOSURE This invention relates to novel anthraquinone dyestuffs and to methods of dyeing and printing of synthetic fibre materials with such dyestuffs.

The novel anthraquinone dyestuffs are compounds of the formula:

atoms; hydroxy, alkoxy, hydroxy-alkylene-oxy, alkoxyal kylene-oxy, alkoxycarbonyl or cyano groups; or by amine groups which may in turn be substituted by alkyl, hydroxyalkyl, alkoxy-alkyl or cyano-alkyl radicals. Examples of the unsubstituted or substituted alkyl groups are the methy, ethyl, propyl, isopropyl, butyl, isobutyl, amyl or.

isoamyl groups; the 2-chloro-, 2-bromo-, 2 hydroxy-', 2- methoXy-, 2-ethoxyor 2-cyano-ethyl radicals; the ethoxycarbonyl-methyl radical; the 3-chloro-, 3-hydroxyor 3- methoxy-propyl groups; the 4-methoxy-butyl radical; the hydroXy-, methoxyor ethoxy-ethyleneoxy-ethyl groups; and the dimethyl-, diethyl-, bishydroxyethyl-, bismethoxyethylor biscyanoethylaminoethyl groups.

If R and/or R stand for alkenyl groups, these are primarily the vinyl propenyl-(l) or or a B-phenyl-ethenyl group.

propenyl -(2) groups If R, and/or-R stand for aralkyl groups, these are preferably benzyl, p-phenyl-e thyl or a-phenyl-propyl radicals which can be substituted by halogen atoms, lower alkyl or alkoxy, carboXy-alkyl or cyano groups.

The aryl radical X is preferably a phenyl radical which can be unsubstituted or monoor poly-substituted. Examples of substituents are: halogen atoms, such as chlorine, bromine, fluorine; alkyl groups with 1, to 12 carbon atoms, which may in turn be substituted by halogen, al-

koxy, cyano or car-boxyalkyl radicals; unsubstituted or",

3,499,896 Patented Mar. 10, 1970 substituted phenyl or aryloxy groups; alkoxy radicals with 1 to 6 carbon atoms which may in turn be substituted by halogen, alkoxy, cyano or carboxyalkyl groups; esterified carboxy groups, sulphonic acid ester or sulphofiuoride groups; trifluoromethyl, acetyl or nitro groups; urethane or urea groups; unsubstituted or substituted sulphonamide radicals; arylazo groups; alkyl or aryl-sulphone radicals; alkylor arylthio radicals or p-alkoxy-carbonyl-ethylene groups.

Specific examples of such substituents for the aryl radical X are the methyl, ethyl, propyl, butyl, isobutyl, t-butyl or amyl groups; a methoxy, or ethoXy-methyl group; a B- methoxyor ethoxy-ethyl radical; a a-methoxyor ethoxypropyl group; the methoxy, ethoxy, propoxy, or butoxy radicals; a methoxy, ethoxyor propoxy-methoxy or -ethoxy group; the methoxyor ethoxycarbonyl-methyl or -ethyl groups; the methoxyor ethoXycarbonyl-methoxy or -ethoXy radicals; a methoxyor ethoxycarbonylamino group; a N-phenylor N-phenyl-N-methyl-sulphonamide radical; a phenylazo group; a methylor phenylsulphonyl or -sulphinyl group; a methyl-, ethyl-, or phenylthio radical; -or the fl-ethoxycarbonyl-ethylene group.

Examples of the novel anthraquinone dyestuffs include the compounds having the following formulas:

where R and R are The dyestufiTs of the present inven.ion can be obtained, for example, in known manner by reacting compounds of the formula in which X has the same meaning as above, with option I ally substituted alkanols, alkenols or aralkanols at 0- 150 C. in the presence of an acid-binding agent, for example, the sodium or potassium derivative of an optionally substituted alkanol, alkenol or aralkanol.

Synthetic fibre materials which can be used are primarily linear aromatic polyesters, for example, polyethylene terephthalates or polyesters obtained from 1,4- b is(hydroxymethyl)-cyclohexane and terephthalic acid, or also fibre materials made of polyamides, polyurethanes, polyacrylonitrile, polyolefines or cellulose triacetate.

Dyeing and printing can be carried out by known methods. The dyestufis are expediently usedin a finely dispersed. form. When dyeing fibres of polyethylene terephthalate, the usual carriers can be added or the dyeing can be carried out at 120145 C. under pressure.

Dyeing or printing is preferably carried out according to the thermosol process in which the printed or padded fibre materials are briefly heated, possibly after an intermediate drying, at temperatures of about 180-230. This heating is generally performed for periods of time ranging from 30 seconds to 2 minutes.

The dyeings and prints obtained with the dyestuffs used according to the invention are characterised by a very good texture, a high dyestuif yield and by excellent fastness to light, thermofixing, washing, rubbing and ironing.

In the following examples the parts means parts by weight unless otherwise stated.

Example 1 (a) A fabric of polyethylene terephthalate fibres is impregnated on a foulard with a liquor containing, per litre, 20 g. 2,4-bis-(p-methoxyethoxy)-6-(4'-phenylamino-1-anthraquinonylamino) 1,3,5 triazine and 10 g.'of a thermosol auxiliary, in particular, a polyether. The fabric is then squeezed to a weight increase of 70% and dried in a suspended nozzle drier or drying cabinet at -l2() C. The fabric is subsequently treated in a stenter or nozzle hot flue with hot air at 190-210 C. for about 45 seconds, then rinsed, reductively aftertreated, if desired, then rinsed and dried. The reductive after-treatment to remove dyestuff particles which superficially adhere to the fibres can be carried out by introducing the fabric at 25 C. into a bath containing 3-5 cc./litre of a sodium hydroxide solution of 38% B and 1-2 g./litre of concentrated hydrosulphite, heating the bath to 70 C. within about 15 minutes and keeping it at 70 C. for a further 10 minutes. The fabric is then rinsed hot, acidified at 50 C. with 23 cc./litre of formic acid, rinsed and dried.

A reddish blue dyeing is obtained which is characterised by a high dyestuff yield, very good texture and ex cellent fastness properties, particularly by very good fastness to thermofixing, washing, rubbing and light.

An analogous dyeing is obtained when the polyethylene terephthalate fibers are replaced with polyester fibres obtained from 1,4-bis-(hydroxymethyl)-cyclohexane and terephthalic acid. Similarly, a reddish blue dyeing is obtained when the polyethylene terephthalate fibres are replaced with cellulose triacetate fibers and thermosolisation is carried out at 215 C., or when polyamide or polyurethane fibres are used and thermosolisation is carried out at 190215 C.

(b) A previously cleaned and thermofixed fabric of polyethylene terephthalate fibres is printed with a printing paste which consists of 40 g. of the dyestuff mentioned in Example 1(a), 475 g. of water, 465 g. crystal gum 1:2 and 20 g. of sulphonated caster oil. The crystal gum may also be replaced with an alginate thickener. The printed and dried material is passed over a high capacity stenter or through a condensation apparatus at 190200 C. in order to fix the dyestutf. The treatment lasts about 3060 seconds. The fixed print thus obtained is subsequently rinsed cold, soaped with 1-2 g./litre of an anion-active detergent at 70-80 C. for about 10 minutes, rinsed first hot and then cold, and dried.

A print is obtained which corresponds to the dyeing of Example 1(a) and is characterised by the same excellent fastness properties. Similarly, a reddish blue print is obtained when the polyethylene terephthalate fibres are replaced with fibres of cellulose triacetate, polyamide or polyurethane.

(c) parts of polyethylene terephthalate fibres are dyed with 1 part of the finely dispersed dyestufi? mentioned in Example 1(a) in 4000 parts of water, in the presence of 15 parts of o-cresotic acid methyl ester as carrier, at 100 C. and pH 4.5 for 1 hours. A reddish blue dyeing is obtained, which is characterised by very good fastness to washing, thermofixing and light. A similar dyeing is obtained when dyeing is carried out in the absence of a carrier at 125l30 C. for 1 hour.

When 100 parts cellulose triacetate are dyed with 1 part of the finely dispersed dyestuff mentioned in Example 1(a) in 3000 parts of water at 100 C. for 1 hour, a reddish blue dyeing of very good fastness to washing, thermofixing and light is again obtained.

The dyestuff mentioned in Example 1(a) can be prepared as follows: a solution of 7.2 parts of 88.1% potassium hydroxide in 110 parts glycol monomethyl ether is mixed at room temperature, While stirring, with 24.9 parts 2,4 dichloro-6-(4'-phenylamino-l-anthraquinonylamino)-1,3,5-triazine, the temperature is allowed to rise, due to the exothermic reaction, to about 50-60" C. and stirring is continued until the dyestutf formation is completed. After cooling, the product which crystallises in the form of dark violet prisms is filtered off with suction, and washed with Water; after drying, there are obtained 29 parts 2,4-bis-(ti-methoxyethoxy)-6-(4-phenylamino- 1' anthraquinonylamino) 1,3,5-triazine, i.e. 96% of theory.

Calc. for C2gH27N505 (541.5) (percent): N, 12.93; 0, 17.72. Found (percent): N, 12.84; 0, 17.61.

Examples 2-17 Reddish blue dyeings r prints of very good fastness to light, washing, rubbing and thermofixing are also obtained when fibres of polyethylene terephthalate, cellulose triacetate, polyamide or polyurethane are dyed according to Example 1(a) or printed according to Example 1(b) with the following dyestuffs which are prepared in analogy with Example 1(d):

Example: Dyestuff 2 2,4-bis-(methoxy)-6-(4-phenylamino-lanthraquinonylamino l ,3 ,5 -triazine.

3 2,4-bis-(n-amyloxy)-6-(4'-phenylaminol-anthraquinonylamino) -1,3 ,5 -triazine.

4 2,4-bis-(B-cyanoethoxy)-6-(4'-phenylamino-l-anthraquinonylamino)-1,3,5- triazine.

5 2,4-bis-(ethoxycarbonylmethoxy)-6-(4'- phenylaminol -anthraquinonylamino 1,3 ,S-triazine.

6 2,4-bis- ,B-hydroxyethoxyethoxy) -6-( 4- phenylaminol-anthraquinonylamino 1,3 ,5 -triazine.

7 2,4-bis-(B-dimethylaminoethoxy)-6-(4'- phenylamino-1-anthraquinonylamino)- 1,3 ,5 -triazine.

8 2,4-bis-(fl-vinyloxy) -6- (4'-phenylaminol-anthraquinonylamino) 1,3,5-triazine. 9 2,4-'bis-(B-allyloxy)-6- (4-phenylamino- 16 2,4-bis- 'y-phenylpropoxy) -6- 4'-phenylamino-l-anthraquinonylamino) -1,3 ,5 triazine.

17 2,4-bis- 8-phenylethoxy) -6- 4'-phenylamino-l-anthraquinonylamino) -l,3,5-

triazine.

8 Example 18 (a) A fabric of Polyethylene terephthalate fibres is dyed according to Example 1(a) with a liquor containing 20 g. 2 (n-amyloxy)-4-(;8-methoxyethoxy)-6-(4' phenylamino-l-anthraquinonylamino)-1,3 ,5 -triazine, and a reddish blue dyeing is thus obtained which exhibits a high dyestuff yield, very good texture and excellent fastness properties, especially very good fastness to thermofixing, washing, rubbing and light. Reddish blue prints are obtained, when polyethylene terephthalate fibres are printed with 2 (n-amyloxy)-4-(B-methoxyethoxy)-6-(4- phenylamino 1 anthraquinonylamino)-1,3,5triazine according to Example 1(b), or when the polyethylene terephthalate fibres are replaced with fibres of polyamide, polyurethane or cellulose triacetate.

The dyestuff mentioned in Example 18(a) can be prepared as follows: a solution of 3.5 parts of 88.1% potassium hydroxide in parts glycol monomethyl ether is mixed at room temperature, while stirring, with 24.9 parts 2,4-dichloro-6-(4-phenylamino-l-anthraquinonylamino) 1,3,5 triazine, the 2-chloro-4-(B-methoxyethoxy) 6-(4 phenylamino-l-anthraquinoylamino)- 1,3,5-triazine, which crystallises after the reaction has subsided and the mixture has cooled, is filtered off with suction and washed with n-amyl alcohol, the product is introduced at room temperature into a solution of 3.7 parts of 88.1% potassium hydroxide in parts of n-amyl alcohol and the mixture is stirred at 80 C. until the dyestuff formation is completed. After cooling, the product which crystallises in the form of violet prisms is filtered off with suction, washed with methanol and water; after drying, there are obtained 29 parts 2-(namyloxy)-4-(,8-methoxyethoxy)-6-(4-phenylamino l anthraquinonylamino)-1,3,5-triazine, i.e. 97% of theory.

Calc. for C H N O (553.5) (percent): N, 12.63; 0, 14.44. Found (percent): N, 12.59; 0, 14.37.

Examples 19-24 Reddish blue dyeings and prints of very good fastness to washing, rubbing and thermofixing are also obtained when fibres of polyethylene terephthalate, cellulose triacetate, polyamide or polyurethane are dyed according to Example 1(a) or printed according to Example 1(b) with the following dyestuffs prepared in analogy with Example 18(b):

Example:

Dyestuif Example 25 (a) A fabric of polyethylene terephthalate fibres is dyed according to Example 1(a) with a liquor containing per litre, 20 g. of a mixture of 2,4-bis-(benzyloxy) and -'y-phenylpropoxy)-6-(4'-phenylamino 1 anthraquinonylamino)-l,3,5-triazine, and there is thus obtained a reddish blue dyeing of excellent dyestuff yield, very good texture and outstanding fastness to thermofixing, washing, rubbing and light. Reddish blue prints are ob- I Example:

tained, when polyethylene terephthalate fibres are printed with the said dyestuif mixture, or when the polyethylene terephthalate fibres are replaced with fibres of polyamide, polyurethane or cellulose triacetate.

(b) The dyestutf mixture described in Example 25 (a) is prepared, for example, as follows: a solution of 21.6 parts of 88.1% potassium hydroxide in 150 parts benzyl alcohol and 175 parts 'y-phenylpropyl alcohol is mixed at room temperature with 74.7 parts 2,4-dichloro-6-(4 phenylamino -1-anthraquinonylamino )-l ,3,5-triazine and the mixture is stirred until the exothermic reaction is completed. After colloing, the blue-violet product is filtered off with suction, and washed with water; after drying, there are obtained 102 parts of a mixture of 2,4-bis-(benzyloxy) and -phenylpropoxy) -6-4'-phenylamino-1- anthraquinonylamino )-1,3,5-triazine.

Examples 26-31 Reddish blue dyeings and prints of very good fastness to washing, rubbing and the thermofixing are also obtained when fibres of polyethylene terephthalate, cellulose triacetate, polyamide or polyurethane are dyed according to Example 1(a) or printed according to Example 1(b) with the following dyestuff mixtures prepared in analogy with Example 25 (b).

Dyestuff mixture consisting of 26 2,4-bis-(isobutoxy)- and -(fi-ethoxy-ethoxy)- 6 4'phenylamino 1 anthraquinonylamino) -1,3,5-triazine.

27 2,4-bis-(B-cyanoethoxy)- and -(benzyloxy)- 6-(4-phenylamino 1 anthraquinonylamino) -1,3,5-triazine.

28 2,4-bis-(p-allyloxy)-and (fl-chloroethoxy)-6- (4 phenylamino 1 anthraquinonylamino)-1,3,5-triazine.

29---- 2,4-bis-(ethoxycarbonylmethoxy)- and -methoxypropoxy)-6-(4' phenylaminol-anthraquinonylamino)-1,3 ,5 -triazine.

30 2,4 bis (benzyloxy)- and -(p-t-butyl'benzyloxy)-6-(4-phenylamino 1 anthraquinonylamino)-1,3,5-triazine.

31 2,4-bis-(,8-phenylethoxy)- and -(fl-phenylethenoxy)-6-(4-phenylamino 1 anthraquinonylamino)-1,3,5-triazine.

Example 32 (a) When a fabric of polyethylene terephthalate fibres is dyed according to Example 1(a) with a liquor containing per litre, 20 g. 2,4-bis-(fl-methoxyethoxy)-6-(4- p-methoxy-phenylamino 1 anthraquinonylamino) 1, 3, S-triazine, a clear blue dyeing is obtained which is characterised by a high dyestuff yield, very good texture and outstanding fastness to light, thermofixing, washing, and ironing. Clear blue prints or dyeings are also obtained when polyethylene terephthalate fibres are printed or dyed according to Example 1(b) or 1(c) with 2,4-bis- (B-methoxy-ethoxy) 6 (4-p-methoxy-phenylamino-1- anthraquinonylamino)-1,3,5-triazine, or when the polyethylene terephthalate fibres are replaced with fibres of polyamide, polyurethane or cellulose triacetate.

(b) The dyestuff mentioned in the present example can be prepared as follows: a solution of 14.5 parts of 86.9% potassium hydroxide in 220 parts of glycol monomethyl ether is mixed at 20-25 C. with 53 parts 2,4- dichloro-6-(4'-p-methoxyphenylamino 1 anthraquinonylamino) 1,3,5 triazine and the mixture is heated at 80 C. for 1 hour. After cooling, the product which crystallises in the form of blue prisms is filtered off with suction and washed with methanol and water; there are obtained 61 parts 2,4'bis-(fi-methoxyethoxy)-6-(4'-pmethoxyphenylamino l anthraquinonylamino) 1,3,5- triazine, i.e. 99.5% of theory.

CHIC. for C30H29N507 N, O,

9 Found: N, 12.30; 0, 19.57.

10 Examples 33-43 Clear blue dyeings or prints of very good fastness to light, washing, rubbing and thermofixing are also obtained, when fibres of polyethylene terephthalate, cellulose triacetate, polyamide or polyurethane are dyed ac cording to Example 1(a) or printed according to Example 1(b) with the following dyestuffs prepared in analogy with Example 32(b):

Example: Dyestuif 33 2,4 bis (ethoxy)-6-(4+p-methoxyphenylamino 1 anthraquinonylamino) 1,3,5- triazine.

2,4 bis (cyclohexoxy) 6-(4'-p-methoxyphenylamino 1 anthraquinonylamino)- 1,3,5-triazine.

2,4 bis (fi-hydroxyethoxy)-6-(4'-p-methoxyphenyl amino 1 anthraquinonylamino) -1,3,5-triazine.

2,4 bis [B-(fiioxethylamino)-ethoxy]-6- (4' p methoxy phenylamino 1 anthraquinonylarnino) -1,3,5-triazine.

2,4 ibis (5 methoxybutoxy) 6 (4-pmethoxyphenylamino 1 anthraquinon-ylamino)-1,3,5-triazine.

2,4 *bis (B-bromoethoxy)- 6-(4-p-methoxyphenylamino 1 anthraquinonylamino)- 1,3,5-triazine.

2,4 bis (p-chlorobenzyloxy)-6-(4'-p-methoxyphenylamino 1 anthraquinonylamino)-1,3,5-triazine.

2,4 bis (m-fluorobenzylox-y)-6-(4-p-methoxyphenylamino 1 anthraquinonylamino)-1,3,5-triazine.

2,4 bis (fi-p-methoxyphenylethoxy)-6-(4'- p methoxyphenylamino 1 anthraquinonylamino) -1,3,5-triazine.

2,4 bis ('y-p-chlorophenylpropoxy)-6-(4- p methoxyphenylamino 1 anthraquinonylamino 1,3,5 -triazine.

2,4 bis (B-phenylethenoxy)-6(4'-p-rnethoxyphenylamino 1 anthraquinonylamino)-1,3,5-triazine.

Examples 44-101 In the following table there are stated the shades which are obtained when fibres of polyethylene terephthalate, cellulose triacetate, polyamide or polyurethane are dyed according to Example 1(a) or printed according to Example 1(b) with the specified dyestuffs or dyestuff mixtures; the dyestuifs can be prepared in analogy with Example 1(d) or 18(d) and the dyestuff mixtures in analogy with Example 25(b):

Example Dyestufi or dyestutf mixture Shade Blue.

Reddish blue.

51 Blue.

Reddish blue.

fonyl methyl ester; sulfonyl phenyl ester; sulfofiuoride; acetyl; nitro; cyano; benzyl; urea; urethane; sulfonamido; methyl sulfonamido phenyl sulfonamido; phenylazo; methyl carbonyl; diphenyl sulfinyl; dimethyl sulfinyl; alkylthio; phenylthio; acetylamino; fl-alkoxycarbonylethylene and alkoxycarbonylamino wherein the alkyl radicals of R contain from 112 carbon atoms.

2. The dyestuif of claim 1, wherein R R or both R and R are alkyl or substituted alkyl radicals of 1 to 6 carbon atoms.

3. The dyestuff of claim 1, wherein R R or both R and R are vinyl, propenyl-l, propenyl-Z, or fi-phenylethenyl.

4. The dyestuff of claim 1, wherein R R or both R and R are benzyl, ,B-phenylethyl or y-phenylpropyl.

5. The dyestuif of claim 4, wherein said R R or both R or R radicals are substituted by 1 to 3 halogen, lower alkyl, lower alkoxy, carboxyalkyl or cyano radicals.

6. The dyestufl of claim 1 having the composition 2,4- bis-(fl-methoxyethyoxy)-6-(4'-phenylamino 1' anthraquinonylamino 1 ,3 ,5 -triazine.

7. The dyestufi of claim 1 having the composition 2,4-

14 bis-(benzyloxy)-6-(4-phenylamino 1 anthraquinonylamino)-1,3,5-triazine.

8. The dyestufi? of claim 1 having the composition 2- (,B-methoxyethoxy) -4- (n-amyloxy) -6- (4-phenylamino-1- anthraquinonylamino) -1,3 ,5 -triazine.

9. The dyestuff of claim 1 having the composition 2,4- bis-(fl-methoxyethoxy)-6-(4'-p-methoxyphenylamino 1- anthraquinonylamino) -1,3 ,5 -triazine.

10. The dyestufi? of claim 1 having the composition 2,4bis-(B-meth0xyeth0xy) -6- (4-p methylphenylamino- 1'-anthraquinonylamino 1,3 ,5 -triazine.

References Cited UNITED STATES PATENTS 2,742,466 4/1956 Randall et al. 260-249 XR 3,349,089 10/1967 Kazankov et al. 260-249 HENRY R. JILES, Primary Examiner JOHN M. FORD, Assistant Examiner US. Cl. X.R. 839, 40, 55, 57

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3.499.896 Dated h 10, 1970 Inventor(s) Rutger Neeff It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

3 6th from the "CH CH O-C N should read top of page CH -CH -0C H 6 12 "means" should read mean 6 l9 2,4-bis-(p-methoxyethoxy)6 (4'-phenyl should read 2,4-bis-(Bmethoxyethoxy)6 (4'-phenyl 8 71 "-Y-phenylpropoxy)" should read (y-phenylpropoxy) 9 l2 "colloing" should read cooling 10 52 "18 (d) should read FORM PO-1050 (IO-69) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,499,896 Dated March 10, 1970 Inventor(s) Rutger Neeff PAGE 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 29.22 2; 322 E552 11 Example 68 "2,4-bis- (cyanoethoxy) ShOllld read 2,4-bis- (Bcyanoethoxy)- l2 Claim 1, "alkyl hydroxyalkyleneoxy" line 62 should read alkyl, hydroxyalkyleneoxy l2 Claim 1, "cyano alkoxy" should read line 70 cyano, alkoxy l2 Claim 1, "phenoxy alkoxy; should read line 71 phenoxy; alkoxy;

l3 Claim 1, sulfonamido phenyl" should line 3 read sulfonamido; phenyl SIGNED AND QEAIEI I I u SEAL) Ana:

mm x. saaunm, m. Attesting Officer commissioner of Patents 1 FORM Po-IoSO (10-69) uscoMM-Dc eosnmee I 11.5 GOVERNMENT PRINTING OFIICi: "II O-lUl-SSI 

